The shape and information content of high-field solid-state proton NMR spectra of methyl groups

The possible variation of the lineshape of the high-field 1H spectrum of methyl groups is explored by simulation and experiment. The spectrum of an isolated methyl group depends, apart from the orientation of the applied field B0 relative to the C3-axis of the group, on its rotational tunnel frequency vt and on its stochastic reorientation rate k. For quantitative analyses, the directional mobility of the C3-axis must also be taken into account. A distinct but frequently occurring case arises when the methyl groups come as pairs of magnetically equivalent close neighbours. For the experiments, single crystals of four compounds I-IV were grown that were isotopically substituted such that they contained protons only in the methyl positions. The crystal symmetry of all compounds I-IV allowed us to record spectra with all methyl groups being orientationally and otherwise equivalent. I, acetonitrile in deuterated hydroquinone, represents the case of a well-isolated methyl group with a "high" tunnel frequency vt. Its spectrum is (almost) independent of the temperature T. In II, monomethyl malonic acid, vt is comparable in size with the strength of the intramolecular dipolar H-H interaction. All seven theoretically expected lines in the 1H spectrum are clearly resolved in the spectra of II. vt can be inferred with an uncertainty of only +/- 300 Hz. vt(T) is found to possess a (flat) maximum near 40 K. Compound III, L-alanine, allows the study of the case of a methyl group with an extremely low, although nonzero tunnel frequency (vt approximately 3 kHz) while IV, dimethylglyoxime, represents the case of a close pair of equivalent methyl groups. Its spectrum reflects intriguing structural implications.     

Optical Particle Sizer: A New Development with Mathematical Correction of Spread Measurement Data

The development of an optical particle sizer for aerosols is described which is based on the principle of light scattering by single particles. The instrument is appropriate for simultaneous measurements of broad particle size distributions and allows applications in hot gases. The main topic concerns the evaluation of the particle size distribution from measured data, i.e. a mathematical correction for the influence of inhomogeneous illumination and of particle shape. Irregularly shaped and randomly orientated particles which also might be illuminated inhomogeneously (laser light, border zone) deliver different signal amplitudes, which finally results in a spreading of the measured particle size distribution. Assuming a specific distribution of signal amplitudes related to every particle size and shape, the spreading of the measured data can be corrected. The mathematical procedure requires the solution of a Fredholm integral equation, i.e. the inversion of a linear equation set whose coefficients are based on a correction function to be determined by a preceding calibration. A new inversion method has been developed combining the well known regularizalion according to Phillips and Twomey and the non-negative least-squares method according to Lawson and Hanson.     

Microstructure rearrangement during the heat-treatment of melt-drawn poly(ethylene terephthalate) fibers

Melt-spun poly(ethylene terephthalate) fibers were isothermally heat-treated at constant length. Microstructural changes occurring during the heat-treatment were monitored using specific gravity, wide-angle x-ray scattering (WAXS), small-angle x-ray scattering (SAXS), optical birefringence, and static mechanical testing. Major changes in the density of the most highly oriented fiber examined occurred in times below 100 ms. For less oriented fibers, the time scale for significant density change increases to the 1–10 s range. The course of birefringence increase approximates that of the density. WAXS measurements show that crystallinity develops at essentially constant crystal perfection, but that the orientation of the crystallites first decreases and then increases with time. SAXS results show development of a four-point pattern, the azimuthal angle of the lobes decreasing with initial orientation, with temperature, and with time. A streak transverse to the fiber axis develops more rapidly than do the lobes. A two-stage transformation process is envisaged, the first stage being the formation of defective crystal fibrils and the second being internal rearrangement of the fibrils to form more perfect crystallites, separated by more amorphous zones. Changes in the crystallite orientation are related to constraints of the noncrystalline material on the crystallites.     

Clusters Beat Trend!? Testing Feature Hierarchy in Statistical Graphics

Graphics are very effective for communicating numerical information quickly and efficiently, but many of the design choices we make are based on subjective measures, such as personal taste or conventions of the discipline rather than objective criteria. We briefly introduce perceptual principles such as preattentive features and gestalt heuristics, and then discuss the design and results of a factorial experiment examining the effect of plot aesthetics such as color and trend lines on participants’ assessment of ambiguous data displays. The quantitative and qualitative experimental results strongly suggest that plot aesthetics have a significant impact on the perception of important features in data displays. Supplementary materials for this article are available online.